Glycerol Dehydration to Acrolein Catalyzed by Silicotungstic Acid: Effect of Mesoporous Support

To facilitate value-added chemical production from renewable glycerol, gas-phase glycerol dehydration to acrolein was conducted using supported silicotungstic acid as solid acid catalysts, focusing on the effects of mesoporous catalyst supports on the catalytic performance. One alumina (Al) support with average mesopore size of 30 nm and two silica supports (Si1254 and Si1252) with mesopore size of 6 nm and 11 nm, respectively, were comparatively evaluated in this study. It was found that the Si1254 silica support with the smallest pore size (6 nm) deactivated the fastest, decreasing both the glycerol conversion and acrolein selectivity along the time-on-stream. The other silica support Si1252 with 11 nm pore size provided an acrolein yield comparable to the Al support over the tested 7.5 h time-on-stream (73.9 mol% for Si1252 vs. 74.1 mol% for Al). However, the mechanisms for achieving the comparable yield are different. Si1252 showed higher acrolein selectivity than Al, but it also deactivated faster than Al due to its quicker coking. On the other hand, Al showed more stable performance in terms of glycerol conversion rate and less coking, but it had lower acrolein selectivity and a higher selectivity to byproducts, especially the undesired byproducts of acetaldehyde and propionaldehyde, which posed difficulties in downstream separation.